Red dye mixtures and their use: dyeing natural or synthetic polyamides

ABSTRACT

The invention relates to a dye mixture containing a dye of the formula ##STR1## in which R 1  is methyl or ethyl and at least one dye of the formulae (2) and (3) ##STR2## in which D is substituted or unsubstituted phenyl, thiophenyl or benzothiazolyl, R 2  is C 1  -C 8  alkyl, R 3  is substituted or unsubstituted C 1  -C 8  alkyl, and R 4  is hydrogen or C 1  -C 4  alkyl, and ##STR3## in which R 5  is C 1  -C 4  alkyl. The dye mixture is distinguished by generally good properties, in particular by good exhaustion.

The present invention relates to mixtures of red-dyeing dyes which aresuitable for the dyeing of natural or synthetic textile polyamide fibrematerial from an aqueous bath and have very good fastness properties andshow good exhaustion expecially in combination with other dyes, inparticular from short liquors.

The present invention relates to a dye mixture containing a dye of theformula ##STR4## in which R₁ is methyl or ethyl and at least one dye ofthe formulae (2) and (3) ##STR5## in which D is substituted orunsubstituted phenyl, thiophenyl or benzothiazolyl, R₂ is C₁ -C₈ alkyl,R₃ is substituted or unsubstituted C₁ -C₈ alkyl and R₄ is hydrogen or C₁-C₄ alkyl, and ##STR6## in which R₅ is C₁ -C₄ alkyl.

The dye mixture according to the invention containing a dye of theformula (1) and a dye of the formula (2) or a dye of the formula (1) anda dye of the formula (3) is preferred.

Examples of suitable R₂ and R₃ radicals in formula (2) as C₁ -C₈ alkylare, independently of one another, methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl andoctyl. R₂ and R₃ are preferably C₁ -C₄ alkyl.

R₃ as C₁ -C₈ alkyl can be substituted, for example, by sulfo, sulfato orphenyl. Examples are benzyl, β-sulfoethyl, γ-sulfopropyl andβ-sulfatoethyl.

Examples of suitable R₄ radicals in formula (2) and R₅ radicals informula (3) as C₁ -C₄ alkyl are, independently of one another, methyl,ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl, inparticular methyl.

D in formula (2) can be substituted, for example, by halogen, such asfluorine, chlorine or bromine, C₁ -C₄ alkyl, such as methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or isobutyl, C₁ -C₄alkoxy, for example methoxy, ethoxy, propoxy or butoxy, C₁ -C₄alkoxycarbonyl, for example methoxycarbonyl or ethoxycarbonyl, sulfo orC₁ -C₄ alkylaminosulfonyl which is unsubstituted or substituted in thealkyl portion by sulfo, for example methylaminosulfonyl,ethylaminosulfonyl or β-sulfoethylaminosulfonyl.

Preference is given to a dye mixture containing at least one dye of theformula (2) in which D is phenyl, thiophenyl or benzthiazolyl, it beingpossible for each of the radicals mentioned to be substituted byhalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl, sulfo or C₁-C₄ alkylaminosulfonyl which is unsubstituted or substituted in thealkyl portion by sulfo, R₂ is C₁ -C₄ alkyl, R₃ is benzyl or C₁ -C₄ alkylwhich is unsubstituted or substituted by sulfo or sulfato, and R₄ ishydrogen or C₁ -C₄ alkyl. In the abovementioned dye mixture, the radicalD of the dye of the formula (2) is preferably phenyl which issubstituted by halogen, sulfo or C₁ -C₄ alkylaminosulfonyl which isunsubstituted or substituted in the alkyl portion by sulfo, orthiophenyl substituted by C₁ -C₄ alkyl or C₁ -C₄ alkoxycarbonyl, orbenzothiophenyl which is unsubstituted or substituted by C₁ -C₄ alkyl,C₁ -C₄ alkoxy or sulfo.

Furthermore, preference is given to a dye mixture containing as dye ofthe formula (3) a dye of the formula ##STR7## in which R₆ is C₁ -C₄alkyl, in particular methyl.

Particular preference is given to a dye mixture containing at least onedye of the formula (2) in which D is phenyl which is substituted bychlorine, sulfo, methylaminosulfonyl, ethylaminosulfonyl orβ-sulfoethylaminosulfonyl, thiophenyl which is substituted by methyl,methoxy- or ethoxycarbonyl, or benzothiophenyl which is unsubstituted orsubstituted by methyl, methoxy or sulfo, R₂ is C₁ -C₄ alkyl, R₃ isbenzyl or C₁ -C₄ alkyl which is unsubstituted or substituted by sulfo orsulfato, and R₄ is hydrogen or C₁ -C₄ alkyl, and/or a dye of the formula(4) in which R₆ is C₁ -C₄ alkyl, in particular methyl.

Very particular preference is given to a dye mixture containing a of theformula (1) in which R₁ is methyl or ethyl, in particular methyl, and atleast one dye of the formula (2) in which D is phenyl which issubstituted by chlorine, sulfo, methylaminosulfonyl, ethylaminosulfonylor β-sulfoethylaminosulfonyl, thiophenyl which is substituted by methyl,methoxy- or ethoxycarbonyl, or benzothiophenyl which is unsubstituted orsubstituted by methyl, methoxy or sulfo, R₂ is ethyl, R₃ is ethyl,β-sulfatoethyl, --(CH₂)₂₋₃ --SO₃ H or benzyl, and R₄ is hydrogen ormethyl, and/or a dye of the formula (4) in which R₆ is methyl.

Particular importance is given to a dye mixture containing a dye of theformula (1) in which R₁ is methyl or ethyl, in particular methyl, and atleast one dye of the formulae (5) to (10) and (4): ##STR8## and a dye ofthe formula (4) in which R₆ is methyl. The particularly important dyemixtures thus contain a dye of the formula (1) and at least one dye ofthe formulae (4), (5), (6), (7), (8), (9) and (10).

A dye mixture containing a dye of the formula (1) in which R₁ is methylor ethyl, in particular methyl, and at least one dye of the formulae(6), (7) or (8) is very particularly important.

In the dye mixtures according to the invention, the ratio of the dyes ofthe formulae (1) to (2) or (3) or the ratio of the dyes of the formulae(1) to (4), (5), (6), (7), (8), (9) or (10) of 10:90 to 90:10 and inparticular 40:60 to 60:40 is preferred. The ratio of the dyes of theformulae (1) to (2) or (3) and in particular the ratio of the dyes ofthe formulae (1) to (4), (5), (6), (7), (8), (9) or (10) of 55:45 to45:55 is very particularly preferred.

The dyes of the formulae (1), (2) and (3) are known per se or can beprepared in analogy to known dyes.

The dye mixture according to the invention can be prepared by mixing theindividual dyes. This mixing process is carried out, for example, insuitable mills, for example ball and pinned-disc mills, and in kneadersor mixers.

Furthermore, the dye mixtures can be prepared by spray-drying of theaqueous dye mixtures.

The invention furthermore relates to a process for the dyeing andprinting of natural or synthetic polyamide materials by means of the dyemixture according to the invention containing the dye of the formula (1)and at least one dye of the formulae (2) and (3). Examples of suitablesynthetic polyamide materials are nylon-6,6 or nylon-6 fibre materialsand an example of a suitable natural polyamide material is wool. Thecustomary dyeing and printing processes are employed for the dyeing andprinting.

The dye mixture containing the dye of the formula (1) and at least onedye of the formulae (2) and (3) is suitable in particular for the dyeingand printing in combination with other dyes and in particular for thedyeing and printing by the trichromatic principle. Trichromatic dyeingis understood as an additive dye mixing of three suitably chosenyellow-, red- and blue-dyeing dyes in the amounts necessary forobtaining the desired shade. The dye mixture according to the inventionis suitable in particular for the dyeing from short liquors, for examplein continuous dyeing processes or batchwise and continuous foam-dyeingprocesses.

The dye mixture according to the invention is distinguished by generallygood properties, for example good solubility, stability of the solutionin the cold, good exhaustion and in particular by good compatibilitywith other dyes and uniformly good exhaustion onto different fibrematerials.

The textile material to be dyed or printed can be present in a widerange of processing forms, for example as fibre, yarn, woven or knittedfabrics and in particular in the form of carpets.

In the dye mixture according to the invention, the dyes of the formulae(1) and (2) or (3) are present either in the form of their free sulfonicacid or preferably as their salts, for example the alkali metal salts,alkaline earth metal salts or ammonium salts or as the salts of anorganic amine. Examples are the sodium salts, lithium salts or ammoniumsalts or the salt of triethanolamine.

As a rule, the dye mixture contains further additives, for examplecommon salt or dextrin.

The dye liquors or printing pastes can also contain further additives,for example wetting agents, antifoams, levelling agents or agentsaffecting the property of the textile material, for example softeningagents, additives for flameproofing or soil-, water- and oil-repellentagents and water-softening agents and natural or synthetic thickeners,for example alginates and cellulose ethers.

In the examples which follow, parts are by weight. The temperaturesgiven are in degrees centrigrade. Parts by weight relate to parts byvolume as the gram relates to the cubic centimeter.

EXAMPLE 1

To prepare the dye mixture containing a dye of the formula ##STR9## anda dye of the formula ##STR10## or a dye of the formulae (101), (102) and(107), in a mixer, a) 30 parts of the dye of the formula (101) and 70parts of the dye of the formula (102) are mixed homogeneously to give100 parts of the mixture which hereinafter is called dye mixture A;

b) 60 parts of the dye of the formula (101) and 40 parts of the dye ofthe formula (104) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture B;

c) 80 parts of the dye of the formula (101) and 20 parts of the dye ofthe formula (103) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture C;

d) 30 parts of the dye of the formula (105) and 70 parts of the dye ofthe formula (101) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture D;

e) 60 parts of the dye of the formula (106) and 40 parts of the dye ofthe formula (101) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture E;

f) 80 parts of the dye of the formula (107) and 20 parts of the dye ofthe formula (101) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture F;

g) 10 parts of the dye of the formula (108) and 90 parts of the dye ofthe formula (101) are mixed homogeneously to give 100 parts of themixture which hereinafter is called dye mixture G;

h) 50 parts of the dye of the formula (101), 25 parts of the dye of theformula (102) and 25 parts of the dye of the formula (107) are mixedhomogeneously to give 100 parts of the mixture which hereinafter iscalled dye mixture H.

EXAMPLE 2

10 parts of a nylon-6,6 fibre material (Helance fabric) are dyed in 500parts of an aqueous liquor containing 2 g/l of ammonium acetate andhaving a pH which has been adjusted to 5 with acetic acid. The dyeswhich are used are 0.12% of the red dye mixture A according to Example1a), 0.27% of the yellow dye of the formula ##STR11## and 0.13% of theblue dye of the formula ##STR12## the amounts given being based on theweight of the fibres. The dyeing time at a temperature of 60° to 98° is30 to 90 minutes. The dyed nylon-6,6 fibre material is then removed fromthe liquor and rinsed and dried as usual. This gives a piece of fabriccompletely levelly dyed in a neutral brown shade having nomaterial-related streaks whatever.

Instead of 0.13% of the dye of the formula (110), it is also possible touse an equimolar amount of the dye C.I. Acid Blue 40, C.I. Acid Blue258, C.I. Acid Blue 288, C.I. Acid Blue 324 or C.I. Acid Blue 336 inExample 2. Likewise, instead of 0.27% of the dye of the formula (109),it is possible to use an equimolar amount of the dye C.I. Acid Yellow199 or C.I. Acid Yellow 219 in Example 2.

EXAMPLES 3 TO 9

Example 2 is repeated, using the dyes of the formulae (109) and (110)listed in Table 1 below and the dye mixtures from Example 1 instead of0.12% of the red dye mixture A and 0.27% of the yellow dye of theformula (109) and 0.13% of the blue dye of the formula (110), to givethe pieces of fabric dyed completely levelly in the shade given.

                  TABLE 1                                                         ______________________________________                                        Example Dyes used               Shade                                         ______________________________________                                        3       0.18% of dye mixture B  reddish                                               0.18% of the dye of the formula (109)                                                                 brown                                                 0.077% of the dye of the formula (110)                                4       0.04% of dye mixture C  olive                                                 0.25% of the dye of the formula (109)                                         0.14% of the dye of the formula (110)                                 5       0.12% of the dye mixture D                                                                            neutral                                               0.27% of the dye of the formula (109)                                                                 brown                                                 0.13% of the dye of the formula (110                                  6       0.17% of dye mixture E  reddish                                               0.18% of the dye of the formula (109)                                                                 brown                                                 0.07% of the dye of the formula (110)                                 7       0.036% of dye mixture F                                                       0.25% of the dye of the formula (109)                                                                 olive                                                 0.124% of the dye of the formula (110)                                8       0.18% of dye mixture G  reddish                                               0.18% of the dye of the formula (109)                                                                 brown                                                 0.08% of the dye of the formula (110)                                 9       0.20% of dye mixture H  reddish                                               0.18% of the dye of the formula (109)                                                                 brown                                                 0.10% of the dye of the formula (110)                                 ______________________________________                                    

The procedure of Example 2 is repeated, except that 0.12% of a red dyemixture consisting of 50 parts of the dye of the formula ##STR13## and50 parts of the dye of the formula (107) is used instead of 0.12% of thered dye mixture A, to give a piece of fabric dyed completely levelly ina neutral brown shade.

EXAMPLE 10

10 parts of a nylon-6,6 yarn are dyed in 400 parts of an aqueous liquorcontaining 1.5 g/l of ammonium acetate and having a pH which has beenadjusted to 5.5 with acetic acid. The dyes which are used are 0.12% ofdye mixture B, 0.27% of the dye of the formula (109) and 0.13% of thedye of the formula (110), the amounts given being based on the weight ofthe fibres. The dyebath is heated to 98° over a period of 30 minutes andmaintained at 96° to 98° for 60 minutes. The dyed yarn is then removedfrom the dyebath and rinsed and dried as usual. This gives a yarn dyedin a neutral brown shade.

EXAMPLE 11: (Exhaust Dyeing Process for Carpets)

A beam dyeing apparatus (laboratory piece-dyeing apparatus, Model 10from Rudolf Then) comprises, as its main parts, a horizontal dye boilerequipped with cooling jacket and connected with a secondary boiler whichcontains a special reversible pump to produce a circulation system.

This dyeing apparatus is entered with a beam charged with a nylon-6 looppile carpet of 50 cm in width, 135 cm in length and a weight of 380 g. 6liters of softened water were poured into the secondary boiler and 60 mlof 2N sodium hydroxide solution were added. By opening the correspondingvalves (secondary boiler and connecting lines, pump/dye boiler), theliquor flows from the secondary boiler by gravity into the dye boiler,while the air displaced flows into the secondary boiler through a ventline. After the dyeing apparatus has been filled, the liquor remainingin the secondary boiler has a height of about 5 cm and then thecirculating pump is turned on. To control the pH, a hole is drilled intothe pipeline between the dye and secondary boiler (direction of flow)and a combination glass electrode is inserted. The dye liquor iscirculating during the entire dyeing process from inside to outside,while the pressure gradient is 0.1 to 0.2 bar, and the delivery of thepump is about 6 liters per minute. The liquor is heated to 98°, and 7.6g of an anionic levelling agent of high fibre affinity, dissolved in 100ml of water, is added to the secondary boiler over a period of 5minutes.

The dyeing temperature is adjusted to 97° to 98° while the pH is 10.7.The pH of the sample removed from the dyebath and cooled to 20° is 11.9.

2.5 g of the red dye mixture B and 1.8 g of the yellow dye of theformula (109), both dissolved in 200 ml of hot water, are run in to thesecondary boiler from a dropping funnel over a period of 10 minutes.After 30 minutes, a total of 100 ml of 1N sulfuric acid are metered inby means of a piston burette at a rate of 5.5 ml per minute over aperiod of 10 minutes and at a rate of 2.25 ml per minute over a furtherperiod of 20 minutes.

After another 10 minutes, the pH is 3.8. The dyebath is exhausted, i.e.more than 99% of the dyes has been absorbed by the material to be dyed.The heating is turned off, and the dye liquor is cooled to 60° by meansof indirect cooling. During this time, the pH increases to 3.9. Thealmost water-clear liquor is pumped back into the secondary boiler, andthe beam is removed. The carpet material is unwound, centrifuged anddried. The nylon-6 loop pile carpet has been dyed uniformly levellyorange.

What is claimed is:
 1. A dye mixture which contains a dye of the formula##STR14## in which R₁ is methyl or ethyl and at least one dye of theformulae (2) and (3) ##STR15## in which D is substituted orunsubstituted phenyl, thiophenyl or benzothiazolyl, R₂ is C₁ -C₈ alkyl,R₃ is substituted or unsubstituted C₁ -C₈ alkyl, and R₄ is hydrogen orC₁ -C₄ alkyl, and ##STR16## in which R₅ is C₁ -C₄ alkyl.
 2. A dyemixture according to claim 1, which contains a dye of the formula (2) inwhich D is phenyl, thiophenyl or benzothiazolyl, in which each of theradicals mentioned can be substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ alkoxycarbonyl, sulfo or C₁ -C₄ alkylaminosulfonyl whichis unsubstituted or substituted in the alkyl portion by sulfo, R₂ is C₁-C₄ alkyl, R₃ is benzyl or C₁ -C₄ alkyl which is unsubstituted orsubstituted by sulfo or sulfato, and R₄ is hydrogen or C₁ -C₄ alkyl. 3.A dye mixture according to claim 1, which contains a dye of the formula##STR17## in which R₆ is C₁ -C₄ alkyl.
 4. A dye mixture according toclaim 1, which contains a dye of the formula (1) in which R₁ is methylor ethyl and a dye of the formula (2) in which D is phenyl which issubstituted by chlorine, sulfo, methylaminosulfonyl, ethylaminosulfonylor β-sulfoethylaminosulfonyl, thiophenyl which is substituted by methyl,methoxy- or ethoxycarbonyl, or benzothiophenyl which is unsubstituted orsubstituted by methyl, methoxy or sulfo, R₂ is ethyl, R₃ is ethyl,β-sulfatoethyl, --(CH₂)₂₋₃ -- SO₃ H or benzyl, and R₄ is hydrogen ormethyl, or a dye of the formula ##STR18## in which R₆ is methyl.
 5. Adye mixture according to claim 4, which contains as dye of the formula(2) at least one dye of the formulae (5) to (10) ##STR19##
 6. A dyemixture according to claim 1, wherein the ratio of the dyes of theformulae (1) to (2) or (1) to (3) is 10:90 to 90:10.
 7. A dyeing orprinting preparation containing a dye mixture according to claim
 1. 8. Anatural or synthetic polyamide material dyed or printed with a dyemixture which contains a dye of the formula ##STR20## in which R₁ ismethyl or ethyl and at least one dye of the formulae (2) and (3)##STR21## in which D is substituted or unsubstituted phenyl, thiophenylor benzothiazolyl, R₂ is C₁ -C₈ alkyl, R₃ is substituted orunsubstituted C₁ -C₈ alkyl, and R₄ is hydrogen or C₁ -C₄ alkyl, and##STR22## in which R₅ is C₁ -C₄ alkyl.
 9. A dye mixture of claim 3wherein R₆ is methyl.
 10. A dye mixture of claim 4 wherein R₁ is methyl.11. A dye mixture of claim 6 wherein the ratio is 40:60 to 60:40.
 12. Adye mixture of claim 6 wherein the ratio is 45:55 to 55:45.
 13. Amaterial of claim 8 which is a textile material.
 14. A method of dyeingor printing a natural or synthetic polyamide material which comprisescontacting the polyamide material with a tinctorally effective amount ofa dye mixture of claim
 1. 15. A method of claim 14 wherein the dyemixture is used in combination with other dyes.
 16. A method for thetrichromatic dyeing of a natural or synthetic polyamide material whichcomprises contacting the polyamide material with a tinctorally effectiveamount of a trichromatic mixture of dyes consisting of a dye mixture ofclaim 1 in combination with at least one yellow or orange dye and atleast blue dye.